EP3096878B1 - Exhaust systemdiesel comprising an oxidation catalyst - Google Patents

Exhaust systemdiesel comprising an oxidation catalyst Download PDF

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Publication number
EP3096878B1
EP3096878B1 EP15701405.1A EP15701405A EP3096878B1 EP 3096878 B1 EP3096878 B1 EP 3096878B1 EP 15701405 A EP15701405 A EP 15701405A EP 3096878 B1 EP3096878 B1 EP 3096878B1
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Prior art keywords
washcoat region
washcoat
catalyst
platinum
zeolite
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EP15701405.1A
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German (de)
English (en)
French (fr)
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EP3096878A1 (en
Inventor
Andrew Francis Chiffey
John Goodwin
James LEELAND
Francois Moreau
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Johnson Matthey PLC
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Johnson Matthey PLC
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    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/00Catalysts
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    • B01D2255/902Multilayered catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
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    • B01D2255/902Multilayered catalyst
    • B01D2255/9022Two layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/903Multi-zoned catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/903Multi-zoned catalysts
    • B01D2255/9032Two zones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/91NOx-storage component incorporated in the catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01DSEPARATION
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    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/912HC-storage component incorporated in the catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • B01D2257/404Nitrogen oxides other than dinitrogen oxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702Hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2330/00Structure of catalyst support or particle filter
    • F01N2330/02Metallic plates or honeycombs, e.g. superposed or rolled-up corrugated or otherwise deformed sheet metal
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N2330/00Structure of catalyst support or particle filter
    • F01N2330/06Ceramic, e.g. monoliths
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N2370/00Selection of materials for exhaust purification
    • F01N2370/02Selection of materials for exhaust purification used in catalytic reactors
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2510/00Surface coverings
    • F01N2510/06Surface coverings for exhaust purification, e.g. catalytic reaction
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2510/00Surface coverings
    • F01N2510/06Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0682Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2510/00Surface coverings
    • F01N2510/06Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0684Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2570/00Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/10Carbon or carbon oxides
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2570/00Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/12Hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2570/00Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14Nitrogen oxides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/10Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

Definitions

  • Oxidation catalysts such as diesel oxidation catalysts (DOCs), typically oxidise carbon monoxide (CO) and hydrocarbons (HCs) in an exhaust gas produced by a diesel engine.
  • Diesel oxidation catalysts can also oxidise some of the nitric oxide (NO) that is present in the exhaust gas to nitrogen dioxide (NO 2 ). Even though nitrogen dioxide (NO 2 ) is itself a pollutant, the conversion of NO into NO 2 can be beneficial.
  • the NO 2 that is produced can be used to regenerate particulate matter (PM) that has been trapped by, for example, a downstream diesel particulate filter (DPF) or a downstream catalysed soot filter (CSF).
  • PM particulate matter
  • DPF downstream diesel particulate filter
  • CSF downstream catalysed soot filter
  • the first washcoat region comprises, or may consist essentially of, a first platinum group metal (PGM) and a first support material.
  • PGM platinum group metal
  • the first washcoat region comprises gold, such as a palladium-gold alloy
  • the first washcoat region comprises a ratio of the total mass of palladium (Pd) to the total mass of gold (Au) of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2.
  • the first washcoat region may further comprise a platinum support material.
  • the first washcoat region may therefore comprise, or consist essentially of, a first PGM, a first support material and a platinum support material.
  • the platinum may be disposed or supported on the platinum support material and the palladium may be disposed or supported on the first support material.
  • the first support material and the platinum support material are preferably different (e.g. different composition).
  • the alumina may be doped with a dopant comprising silicon (Si), magnesium (Mg), barium (Ba), lanthanum (La), cerium (Ce), titanium (Ti), or zirconium (Zr) or a combination of two or more thereof.
  • the dopant may comprise, or consist essentially of, an oxide of silicon, an oxide of magnesium, an oxide of barium, an oxide of lanthanum, an oxide of cerium, an oxide of titanium or an oxide of zirconium.
  • the dopant comprises, or consists essentially of, silicon, magnesium, barium, cerium, or an oxide thereof, particularly silicon, or cerium, or an oxide thereof. More preferably, the dopant comprises, or consists essentially of, silicon, magnesium, barium, or an oxide thereof; particularly silicon, magnesium, or an oxide thereof; especially silicon or an oxide thereof.
  • the first support material, or refractory metal oxide thereof may comprise, or consist essentially of, an alkaline earth metal aluminate.
  • alkaline earth metal aluminate generally refers to a compound of the formula MAl 2 O 4 where "M” represents the alkaline earth metal, such as Mg, Ca, Sr or Ba.
  • M represents the alkaline earth metal, such as Mg, Ca, Sr or Ba.
  • Such compounds generally comprise a spinel structure.
  • the first washcoat region comprises a total weight of the alkaline earth metal that is greater than the total weight of the platinum (Pt).
  • the first washcoat region does not comprise rhodium, an alkali metal and/or an alkaline earth metal, particularly an alkali metal and/or alkaline earth metal disposed or supported on a support material (e.g. the first support material, the platinum support material and/or the palladium support material).
  • a support material e.g. the first support material, the platinum support material and/or the palladium support material.
  • the first washcoat region may not comprise rhodium, an alkali metal and/or an alkaline earth metal, particularly an alkali metal and/or alkaline earth metal disposed or supported on a support material.
  • the second washcoat region may further comprise a zeolite catalyst, such as a zeolite catalyst as herein defined below.
  • a zeolite catalyst such as a zeolite catalyst as herein defined below.
  • the second washcoat region does not comprise cerium oxide or a mixed or composite oxide thereof, such as (i) a mixed or composite oxide of cerium oxide and alumina and/or (ii) a mixed or composite oxide of cerium oxide and zirconia.
  • the first washcoat region may be disposed or supported on the third washcoat region (e.g. see Figure 6 ).
  • the second washcoat region may also be disposed or supported on the third washcoat region.
  • the third washcoat region may be a third washcoat layer, the first washcoat region is a first washcoat zone and the second washcoat region is a second washcoat zone.
  • the second washcoat zone may be in contact with the first washcoat zone [i.e. the second washcoat zone is adjacent to, or abuts, the first washcoat zone].
  • the first washcoat zone and the second washcoat zone may be separated (e.g. by a gap).
  • the third washcoat region may be a third washcoat layer or a third washcoat zone.
  • the third washcoat zone may be disposed or supported on the second washcoat zone (e.g. see Figure 7 ).
  • the first washcoat region is a first washcoat zone.
  • the third washcoat zone may be in contact with the first washcoat zone [i.e. the third washcoat zone is adjacent to, or abuts, the first washcoat zone].
  • the first washcoat zone and the third washcoat zone may be separated (e.g. by a gap).
  • the third washcoat zone typically has a length of 10 to 90 % of the length of the substrate (e.g. 10 to 45 %), preferably 15 to 75 % of the length of the substrate (e.g. 15 to 40 %), more preferably 20 to 70 % (e.g. 30 to 65 %, such as 25 to 45 %) of the length of the substrate, still more preferably 25 to 65 % (e.g. 35 to 50 %).
  • the zeolite catalyst comprises, or consists essentially of, a noble metal and a zeolite.
  • Zeolite catalysts can be prepared according to the method described in WO 2012/166868 .
  • the zeolite is a large pore zeolite.
  • the large pore zeolite preferably has a Framework Type selected from the group consisting of CON, BEA, FAU, MOR and EMT, more preferably BEA.
  • the substrate is made or composed of cordierite (SiO 2 -Al 2 O 3 -MgO), silicon carbide (SiC), Fe-Cr-AI alloy, Ni-Cr-AI alloy, or a stainless steel alloy.
  • the substrate may be of any shape or size. However, the shape and size of the substrate is usually selected to optimise exposure of the catalytically active materials in the catalyst to the exhaust gas.
  • the substrate may, for example, have a tubular, fibrous or particulate form.
  • suitable supporting substrates include a substrate of the monolithic honeycomb cordierite type, a substrate of the monolithic honeycomb SiC type, a substrate of the layered fibre or knitted fabric type, a substrate of the foam type, a substrate of the crossflow type, a substrate of the metal wire mesh type, a substrate of the metal porous body type and a substrate of the ceramic particle type.
  • a fourth exhaust system embodiment comprises the oxidation catalyst in accordance with the invention, preferably as a DOC, and a selective catalytic reduction filter (SCRFTM) catalyst.
  • SCRFTM selective catalytic reduction filter
  • the oxidation catalyst is typically followed by (e.g. is upstream of) the selective catalytic reduction filter (SCRFTM) catalyst.
  • a nitrogenous reductant injector may be arranged between the oxidation catalyst and the selective catalytic reduction filter (SCRFTM) catalyst.
  • the oxidation catalyst may be followed by (e.g. is upstream of) a nitrogenous reductant injector, and the nitrogenous reductant injector may be followed by (e.g. is upstream of) the selective catalytic reduction filter (SCRFTM) catalyst.
  • an ASC catalyst can be disposed downstream from the SCR catalyst or the SCRFTM catalyst (i.e. as a separate substrate monolith), or more preferably a zone on a downstream or trailing end of the substrate monolith comprising the SCR catalyst can be used as a support for the ASC.
  • substantially free of as used herein with reference to a material, typically in the context of the content of a washcoat region, a washcoat layer or a washcoat zone, means that the material in a minor amount, such as ⁇ 5 % by weight, preferably ⁇ 2 % by weight, more preferably ⁇ 1 % by weight.
  • the expression “substantially free of” embraces the expression “does not comprise”.
  • Example 2 The method of Example 1 was repeated, except that soluble platinum salt was added followed by manganese nitrate before stirring the mixture to homogenise.
  • the Pt loading on the part was 1.06 g/L (30 g ft -3 ).
  • the manganese loading on the part was 1.41 g/L (40 g ft -3 ).
  • the weight ratio of Pt to manganese was 3:4.
  • Pd nitrate was added to slurry of small pore zeolite with CHA structure and was stirred. The slurry was applied to a cordierite flow through monolith having 62 cells cm -2 (400 cells per square inch) structure using established coating techniques. The coating was dried and calcined at 500°C. A coating containing a Pd-exchanged zeolite was obtained. The Pd loading of this coating was 1.41 g/L (40 g ft -3 ).
  • Pd nitrate was added to slurry of small pore zeolite with CHA structure and was stirred. The slurry was applied to a cordierite flow through monolith having 62 cells cm -2 (400 cells per square inch) structure using established coating techniques. The coating was dried and calcined at 500°C. A coating containing a Pd-exchanged zeolite was obtained. The Pd loading of this coating was 1.41 g/L (40 g ft -3 ).
  • a second slurry was prepared using a 5% manganese supported on a silica-alumina powder milled to a d 90 ⁇ 20 micron. Soluble platinum salt was added and the mixture was stirred to homogenise. The slurry was applied to the outlet end of the flow through monolith using established coating techniques. The coating was then dried.
  • a third slurry was prepared using a silica-alumina powder milled to a d 90 ⁇ 20 micron. Appropriate amounts of soluble platinum and palladium salts were added followed by beta zeolite such that the slurry comprised 75% silica doped alumina and 25% zeolite by mass. The slurry was then stirred to homogenise. The resulting washcoat was applied to the inlet channels of the flow through monolith using established coating techniques. The part was then dried and calcined at 500°C. The Pt loading of the finished part was 1.80 g/L (51 g ft -3 ) and the Pd loading was 1.68 g/L (47.5 g ft -3 ).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Processes For Solid Components From Exhaust (AREA)
EP15701405.1A 2014-01-23 2015-01-23 Exhaust systemdiesel comprising an oxidation catalyst Active EP3096878B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB1401115.9A GB201401115D0 (en) 2014-01-23 2014-01-23 Diesel oxidation catalyst and exhaust system
GBGB1405871.3A GB201405871D0 (en) 2014-01-23 2014-04-01 Diesel oxidation catalyst and exhaust system
PCT/GB2015/050146 WO2015110818A1 (en) 2014-01-23 2015-01-23 Diesel oxidation catalyst and exhaust system

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EP3096878A1 EP3096878A1 (en) 2016-11-30
EP3096878B1 true EP3096878B1 (en) 2019-05-22

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EP15701405.1A Active EP3096878B1 (en) 2014-01-23 2015-01-23 Exhaust systemdiesel comprising an oxidation catalyst
EP15701406.9A Active EP3096875B1 (en) 2014-01-23 2015-01-23 Exhaust system comprisng a diesel oxidation catalyst
EP15701404.4A Active EP3096872B1 (en) 2014-01-23 2015-01-23 Diesel oxidation catalyst

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EP15701404.4A Active EP3096872B1 (en) 2014-01-23 2015-01-23 Diesel oxidation catalyst

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US (9) US9849423B2 (enExample)
EP (3) EP3096878B1 (enExample)
JP (4) JP6594322B2 (enExample)
KR (4) KR20160111966A (enExample)
CN (3) CN106413892B (enExample)
BR (3) BR112016016925B1 (enExample)
DE (3) DE102015100984B4 (enExample)
GB (12) GB201401115D0 (enExample)
RU (3) RU2733407C2 (enExample)
WO (3) WO2015110817A1 (enExample)

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US10821401B2 (en) 2020-11-03
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